Organic materials having meta, para-isopropylidene diphenoxy units and method

ABSTRACT

Meta,para-isopropylidene bisphenol is homopolymerized and copolymerized to produce a variety of high performance thermoplastics having improved processing characteristics. In addition to polycarbonates, there are provided polyesters, polyestercarbonates, polyepoxides, polysulfones, polyetherimides, polyformals, epoxy resins and polycarbonate-polydiorganosiloxane block polymers.

BACKGROUND OF THE INVENTION

Polycarbonates have been used in a wide variety of applicationsrequiring high performance thermoplastic materials. Althoughpolycarbonates consisting essentially of chemically combined units ofthe formula, ##STR1## has been satisfactorily molded at temperaturesexceeding 250° C., or injection molded to plastic foams at temperaturesexceeding 300° C. using particular blowing agents, the use of suchpolycarbonates, or the employment of additional blowing agents has beensomewhat restricted due to the high temperature polycarbonate shapingrequirements. It is also known, for example, that polycarbonateconsisting essentially of chemically combined units of formula (1) has aglass transition temperature of 150° C. while the correspondingpolycarbonate derived from ortho,para-bisphenol-A has a glass transitiontemperature of 142° C. Continued efforts have been made by the organicthermoplastics industry to improve the flow characteristics ofpolycarbonates and other organic thermoplastics having chemicallycombined isopropylidene bisphenol units.

STATEMENT OF THE INVENTION

In my copending application Ser. No. 966,895, filed Dec. 6, 1978 andassigned to the same assignee as the present invention, there is shownmeta,para-isopropylidene bisphenol of the formula ##STR2## where R isselected from the class consisting of C.sub.(1-8) alkyl radicals,C.sub.(1-6) alkoxy radicals, X is selected from halogen, a is a wholenumber equal to 0 to 4 inclusive, b is a whole number equal to 0 to 3inclusive and the sum of a and b is equal to 0 to 4 inclusive.

I have found that meta,para-isopropylidene bisphenol included within thescope of formula (2) can be polymerized to a polycarbonate having anM_(w) of 72,175, an M_(n) of 13,380 and a glass transition temperatureof 112° C.

DESCRIPTION OF THE INVENTION

There is provided by the present invention, a method for makingpolycarbonates having at least three mole percent of chemically combinedbisphenol units of the formula, ##STR3## based on the total moles ofchemically combined bisphenol units, which comprises,

(A) phosgenating a mixture comprising from 3 to 100 mole percent of abisphenol of formula (2) and from 0 to 97 mole percent of a bisphenol ofthe formula, ##STR4## to produce a polycarbonate, and

(B) effecting the separation of the polycarbonate from the mixture of(A),

where R, X a and b are as previously defined.

Bisphenols included by formula (3) are, for example, ##STR5##

In a further aspect of the present invention, there are providedaromatic polyformals consisting essentially of ##STR6## chemicallycombined with 0 mole percent to 97 mole percent of units of the formula,##STR7##

In addition, there are provided aromatic polysulfones consistingessentially of chemically combined units of the formula, ##STR8## whereR, X, a and b are as previously defined.

Another aspect of the present invention is directed to aromaticpolyesters consisting essentially of chemically combined units of theformula, ##STR9## where R, X, a and b are as previously defined.

An additional aspect of the present invention is directed to bisimidesof the formula, ##STR10## where R, X, a and b are as previously definedand R¹ is selected from C.sub.(1-8) alkyl radicals and C.sub.(6-12) arylradicals.

The bisimides of formula (9) can be made by the procedure of Heath et alU.S. Pat. No. 3,879,428, assigned to the same assignee as the presentinvention. A nitro phthalimide ##STR11## can reacted with a bisphenoxideof the formula, ##STR12## to produce a bisimide within formula (8),where R, X, R¹, a and b are as previously defined and M is an alkalimetal ion such as sodium.

The bisimide of formula (9) can thereafter be hydrolyzed to produce thedianhydride of the formula, ##STR13## where R, X, a and b are aspreviously defined. Polyetherimides also can be made from thedianhydride by a melt polymerization procedure, or an organic solventsolution polymerization with an organic diamine of the formula,

    NH.sub.2 R.sup.2 NH.sub.2,

in accordance with Takekoshi et al U.S. Pat. Nos. 3,803,085 and3,991,004, where R² is a divalent organo radical selected from the classconsisting of (a) aromatic hydrocarbon radicals having from 6-20 carbonatoms and halogenated derivatives thereof, (b) alkylene radicals,C.sub.(2-8) alkylene terminated polydiorganosiloxane cycloalkyleneradicals having from 2-20 carbon atoms, and (c) divalent radicalsincluded by the formula, ##STR14## where Q is a member selected from theclass consisting of ##STR15## --C_(x) H_(2x) -- and x is a whole numberfrom 1 to 5 inclusive, and m is 0 or 1.

The polyetherimides of the present invention consist essentially ofchemically combined units of the formula, ##STR16## where R, X, a, b andR² are as previously defined.

In addition to para,para-bisphenol of formula (4), themeta,para-bisphenol of formula (2) also can be copolymerized with1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene. The meta,para-bisphenolof formula (2) or mixtures thereof with p,p-bisphenol-A also can be usedto make polycarbonate-organopolysiloxane block polymers by effectingreaction in the presence of an acid acceptor between one or more molesof the m,p-bisphenol of formula (2) and a chlorine chain-stoppedpolydiorganosiloxane of the formula, ##STR17## where R³ is a monovalentorganic radical selected from methyl, ethyl, propyl, vinyl, phenyl,chlorophenyl, perfluoropropyl, cyanoethyl and mixtures thereof and n hasan average value of 5-200 inclusive. A typical procedure is shown byVaughn U.S. Pat. No. 3,189,602, assigned to the same assignee as thepresent invention.

The above aromatic organic polymeric materials can have an intrinsicviscosity in methylene chloride at 25° C. of at least 0.1 and preferablyat least 0.3 and are selected from polycarbonates consisting essentiallyof formula (3) units, copolymers consisting eseentially of formula (1)and (3) units, polyesters, polyestercarbonates, polyformals,polyetherimides, polysulfones and polycarbonate-polydiorganosiloxaneblock polymers, etc. The organic polymeric materials can have at least 3mole percent to 100 mole percent of chemically combined units of formula(3) and preferably from 10 to 100 mole percent of such units. Theseorganic polymeric materials can be injection molded to a variety ofshapes, transformed into high performance shaped foams, used in formingplastic sheets, laminates, etc. The organic polymers having chemicallycombined formula (3) units have improved processing characteristics andcan be reinforced with various particulated fillers such as glassfibers, silica fillers, carbon whiskers, up to 50 percent by weight ofthe resulting total blend. Reinforcement of polymer can be accomplishedprior to polymer formation by effecting polymerization in the presenceof filler. Melt blending and solution blending also can be employed.

In order that those skilled in the art will be better able to practicethe invention, the following examples are given by way of illustrationand not by way of limitation. All parts are by weight.

EXAMPLE 1

A mixture of 5 parts of phenol, 1 part of meta-isopropenyl phenol andabout 21 parts of toluene was added dropwise to about 5 parts of a 75%aqueous solution of sulfuric acid. When the addition was completed, thereaction mixture was stirred an additional 5 minutes, diluted with about35 parts of diethylether resulting in the separation of 2 layers. Theorganic layer was washed with about 25 parts of a saturated aqueoussodium bicarbonate solution, dried over magnesium sulfate andconcentrated under reduced pressure. There was obtained a brown oilwhich was crystallized from chloroform resulting in an 81% yield of awhite powder having a melting point of 97°-98° C. Based on method ofpreparation and its IR spectrum, the product wasmeta,para-isopropylidene bisphenol of the formula, ##STR18##

Phosgene was introduced into a mixture over a 20 minute period of 2parts of the above meta,para-bisphenol, 22 parts of methylene chloride,about 7 parts of water, about 0.04 part of triethylamine and 0.016 partof phenol. There was added a total of 0.9 part of phosgene while themixture was agitated along with a sufficient amount of an aqueous sodiumhydroxide solution to maintain the reaction mixture at a pH of 10-12.After the phosgene addition, the mixture was flushed with nitrogen andwashed once with about 25 parts of a 10% hydrochloric acid solution. Themixture was then blended with about 100 parts of methanol resulting inthe precipitation of product. The product was recovered by vacuumfiltration and dried under vacuum at 65° C. for 18 hours. Based onmethod of preparation the product was a polycarbonate consistingessentially of chemically combined units of the formula, ##STR19## andchain terminated with phenoxy units. The product was found to be avaluable injection moldable thermoplastic material having a glasstransition temperature of about 112° C. Those skilled in the art knowthat the polycarbonate has improved processing characteristics ascompared to para,para-isopropylidene bisphenol polycarbonate having aglass transition temperature of about 150° C.

EXAMPLE 2

A mixture of 3.5 parts of the meta,para-bisphenol-A of Example 1, 3.5parts of para,para-bisphenol-A, 16 parts of water, about 26 parts ofmethylene chloride, about 0.03 part of triethylamine, and 0.072 part ofphenol was phosgenated over a 20 minute period. During phosgenation 3.4parts of phosgene was introduced and sufficient 20% aqueous sodiumhydroxide solution to maintain the reaction mixture at a pH in the rangeof 10-11.5. After phosgenation, the organic layer was separated from themixture and added dropwise to about 240 parts of methanol in a blender.There was obtained a precipitated polymer which was recovered by vacuumfiltration and redissolved in methylene chloride and reprecipitated frommethanol. Based on method of preparation, the product was a copolymerconsisting essentially of meta,para-isopropylidene bisphenoxy unitschemically combined with para,para-isopropylidene bisphenoxy units whichwere present in about equal molar amounts. The polymer had an M_(w) of29,204, an M_(n) of 10,785 and T_(g) of 130° C. Those skilled in the artwould know that the processing characteristics of the aforementionedcopolymer with respect to its ability to be molded to various partswould be superior to a polycarbonate consisting essentially ofchemically combined para,para-isopropylidene bisphenoxy units having aglass transition temperature of 150° C.

EXAMPLE 3

There was added with stirring 1.7 part of sodium hydroxide to a mixtureof 4.54 parts of meta,para-bisphenol-A, 0.0459 part of 4-t-butyl phenol,about 8.2 parts of methylene chloride and about 10.2 parts ofN-methylpyrrolidone. The reaction mixture was refluxed for 5 hours at90° C. The reaction mixture was then cooled slightly and poured intoabout 120 parts of methanol in a blender. The product which precipitatedwas collected by vacuum filtration, dissolved in about 20 parts ofmethylene chloride and reprecipitated with about 120 parts of methanolfollowed by drying at 70° C. under vacuum for 16 hours. There wasobtained a polyformal having an M_(w) of 49,700, and M_(n) of about15,560 and a glass transition temperature of 55° C. The polyformal wasfound to be a valuable thermoplastic injection moldable materialreinforceable with a variety of inert materials and useful in a varietyof applications, such as for organic solvent resistant wire coatingformulations.

EXAMPLE 4

A mixture of 7 parts of meta,para-bisphenol-A, 16.6 parts ofdimethylsulfoxide and 45 parts of chlorobenzene was stirred and heatedto 70° C. to produce a clear solution. Nitrogen was then bubbled intothe mixture and about 3.2 parts of a 50% aqueous sodium hydroxidesolution was added during a 5 minute period resulting in a ratio ofabout 2 moles of sodium hydroxide per mole of the meta,para-bisphenol-A.The mixture was then brought to reflux and the solvent was distilledfrom the mixture until the pot temperature reached a 160° C. There wasthen added a 50% solution of 8.81 parts of 4,4'-dichlorodiphenylsulfoneand chlorobenzene at such a rate to maintain the temperature of themixture at least 150° C. The resulting mixture had an equal molar amountof sulfone and bisphenol and the stirring of the mixture continued for 2hours at 150°-160° C. The polymerization was terminated by passingmethyl chloride gas into the mixture until it faded to a light ambercolor. The mixture was then cooled to room temperature and diluted with133 parts of methylene chloride and precipitated twice from methanol.Based on method of preparation there was obtained a polysulfone havingan M_(w) or 49,153, an M_(n) of 23,293 and a glass transitiontemperature of 142° C. It was found that the corresponding polysulfonehaving chemically combined para,para-isopropylidene bisphenol units hasa glass transition temperature of 190° C. Those skilled in the art wouldknow that the polysulfone made in accordance with the practice of thepresent invention has improved processing characteristics andconvertible to a variety of high performance shapes and parts bystandard injection molding techniques.

EXAMPLE 5

Phosgene is introduced into a mixture at a rate of 3.5 parts of phosgeneper hour consisting of 77.75 parts of meta,para-bisphenol-A, 136.9 partsof a bisphenol-A terminated polydimethylsiloxane having an average of 15dimethylsiloxy units, 330 parts of chloroform, 0.6 part of phenol, 0.9part of sodium gluconate, 2.14 parts of triethylamine and 1400 parts ofwater. During the phosgenation, aqueous sodium hydroxide is added to themixture to maintain a pH of about 11.

After the mixture is stirred for 27 minutes, the phosgene flow rate isreduced to about 1 part per minute and continued until the entire amountof base is consumed, which includes 144 parts of sodium hydroxide addedas an aqueous mixture. The total reaction time is 111 minutes. Nitrogenis then bubbled into the two phase mixture to remove any residualphosgene. The reaction mixture is then diluted with an equal volume ofchloroform and the aqueous layer is separated and discarded. The organiclayer is washed with deionized water having a pH of 6.7 and aqueous HCLhaving a pH of 2.0 and thereafter four times with deionized water. Theorganic layer is washed with additional water until it is chloride free,based on a silver nitrate test. The organic layer is then dried overmagnesium sulfate and filtered. The resulting clear solution is thenadded over a 30 minute period to a well stirred mixture of acetone andmethanol to effect the precipitation of product. There is obtained afibrous polymer which is filtered and pressed dry and then washed withadditional acetone-methanol solution and refiltered. Based on method ofpreparation, there is obtained a block polymer containing about 30% byweight of dimethylpolysiloxane and about 70% by weight of polycarbonate.The block polymer is useful as for making semi permeable membranes.

EXAMPLE 6

A mixture of 20.52 parts of meta,para-bisphenol-A, 38.97 parts of4-nitro,N-methylphthalimide, 7.92 parts of sodium hydroxide, 101 partsof dimethylformamide and 58.5 parts of toluene is heated at reflux undera nitrogen atmosphere. The pot temperature during this period is 125° C.The mixture is heated for 6 hours and then refluxed for an additionaltwo hours and allowed to cool to 100° C. Toluene is then removed underreduced pressure and the mixture is allowed to cool to room temperature.There is obtained a precipitate. The mixture is then diluted with about300 parts of ethanol and filtered. There is obtained a white solid afterthe precipitate is washed with water and dried. The yield of product isabout 90%. Based on method of the preparation the product is a bisimideof the formula, ##STR20##

A mixture of 93 parts of the above bisimide and 52.25 parts of sodiumhydroxide, and 260 parts of water is heated to reflux. Methylamine isdistilled along with water at a rate of about 80 parts per hour andfresh water is added to the mixture. A mixture is heated for a total of20 hours and the mixture is allowed to cool slowly. There is obtained asolid which is isolated by filtration in a centrifuge. Based on methodof preparation there is formed tetra-acid having the formula, ##STR21##

A mixture of 45 parts of the above tetra-acid, 30 parts of aceticanhydride and 217 parts of toluene is heated to reflux and held atreflux for 1 hour. The filtrate is allowed to cool slowly. There isobtained a crystalline dianhydride having the following formula,##STR22##

EXAMPLE 7

A mixture of 5.0205 parts of meta,para-bisphenol-A dianhydride ofExample 6, 1.47 part of metaphenylenediamine and 0.089 part of phthalicanhydride is stirred and heated under a nitrogen atmosphere. Theresulting viscous melt is further heated at 280° C. for 1 hour. There isobtained upon cooling a tough clear amber colored material. Based onmethod of preparation the product is a polyetherimide consistingessentially of chemically combined units of the formula, ##STR23##

The above polyetherimide is injection molded to a finished shaperesulting in a tough solvent resistant structure.

EXAMPLE 8

A mixture is phosgenated consisting of 3.5 parts of m,p-bisphenol-A,4.31 parts of 1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene, 16 parts ofwater, 39 parts of methylene chloride, 0.040 part of triethylamine and0.027 part of phenol. There is added 3.4 parts of phosgene andsufficient 20% aqueous sodium hydroxide solution during the 20 minutephosgenation period to maintain the pH of the mixture in the range of10-11.5. The reaction mixture is then allowed to separate into 2 layersand the organic layer is added dropwise to about 250 parts of methanolwhile it is rapidly agitating. There is obtained a precipitated productwhich is collected by vacuum filtration. Based on method of preparationthe product is a polycarbonate copolymer consisting essentially ofchemically combined units of the formula, ##STR24##

A solution of the above copolymer in methylene chloride is cast onto aglass plate. The resulting film is found to be a tough thermoplasticexhibiting flame retardant properties.

EXAMPLE 9

There was added a solution of 3 parts of sodium laurylsulfate in 12parts of water to a solution while it was stirred of 4.56 parts ofmeta,para-bisphenol-A and 1.6 part of sodium hydroxide in 120 parts ofwater. There was then added to the resulting mixture a solution of 4.06parts of terephthaloyl chloride in about 90 parts of chloroform. Anemulsion was formed from the resulting mixture which was stirred anadditional 5 minutes. The reaction mixture was then poured into 500parts of acetone to effect the precipitation of product which wascollected and washed well with water. The product was thenreprecipitated. There was obtained a polyester having a glass transitiontemperature of 150° C., an M_(w) of 54,834 and an M_(n) of 36,999. Basedon method of preparation the product consists essentially of chemicallycombined units of the formula, ##STR25##

The above polyester is found to be injection moldable and convertible toa high strength material.

Although the above examples are directed to only a few of the very manythermoplastic organic materials which can be made in accordance with thepractice of the present invention, it should be understood that thepresent invention is directed to a much broader variety of thermoplasticmaterials based on the use of bisphenols of formula (2) alone or incombination with various other materials which are described in thespecification preceding these examples. Included are, for example, epoxyresins consisting essentially of units derived from the diglycidyl etherof meta,para-isopropylidene bisphenol.

What I claim as new and desire to secure by Letters Patent of the UnitedStates is:
 1. Thermoplastic polycarbonates having improved flowcharacteristics and chemically combined units of the formula, ##STR26##2. A thermoplastic organic polycarbonate, consisting essentially ofchemically combined meta,para-isopropylidene bisphenoxy units andpara,para-isopropylidene bisphenoxy units.
 3. An organic polycarbonatehaving at least 3 mole percent of chemically combinedmeta,para-isopropylidene bisphenoxy units.
 4. A thermoplastic organicpolycarbonate, having substantially equal molar amounts ofmeta,para-isopropylidene bisphenoxy units and para,para-isopropylidenebisphenoxy units.
 5. In a method for making thermoplastic organicpolycarbonates by phosgenating a p,p-bisphenol of the formula, ##STR27##resulting in the production of polycarbonates consisting essentially ofchemically combined units of the formula, ##STR28## having moldingtemperatures exceeding 250° C., the improvement which comprisesphosgenating a mixture comprising p,p-bisphenol and from 3-100 molepercent of a m,p-bisphenol of the formula, ##STR29## whereby apolycarbonate is obtained having improved flow characteristics, where Ris selected from the class consisting of C.sub.(1-8) alkyl radicals,C.sub.(1-6) alkoxy radicals, X is a halogen radical, a is a whole numberequal to 0 to 4 inclusive, b is a whole number equal to 0 to 3 inclusiveand the sum of a and b is equal to 0 to 4 inclusive.
 6. A process inaccordance with claim 5, where the phosgenated mixture consistsessentially of equal molar amounts of meta,para-isopropylidene bisphenoland para,para-isopropylidene bisphenol.